Advances in Solid-State Lasers: Development and Applications_1 doc

3 pump wavelength of 941 nm and laser wavelength of 1030 nm Fan 1993 of Yb:YAG gain medium and easy growth of high quality and moderate concentration crystal without concentration quench

Development and Applications

Advances in Solid-State Lasers: Development and Applications

Edited by

Mikhail Grishin

Intech

Published by Intech

Intech

Olajnica 19/2, 32000 Vukovar, Croatia

Abstracting and non-profit use of the material is permitted with credit to the source Statements and opinions expressed in the chapters are these of the individual contributors and not necessarily those of the editors or publisher No responsibility is accepted for the accuracy of information contained in the published articles Publisher assumes no responsibility liability for any damage or injury to persons or property arising out of the use of any materials, instructions, methods or ideas contained inside After this work has been published by the Intech, authors have the right to republish it, in whole or part, in any publication of which they are an author or editor, and the make other personal use of the work

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First published February 2010

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Cover designed by Dino Smrekar

Advances in Solid-State Lasers: Development and Applications, Edited by Mikhail Grishin

p cm

ISBN 978-953-7619-80-0

Preface

Invention of the solid-state laser has initiated the beginning of the laser era Performance of solid-state lasers improved amazingly during five decades Nowadays, solid-state lasers remain one of the most rapidly developing branches of laser science and become an increasingly important tool for modern technology

This book represents a selection of chapters exhibiting various investigation directions

in the field of solid-state lasers and the cutting edge of related applications The materials are contributed by leading researchers and each chapter represents a comprehensive study reflecting advances in modern laser physics Considered topics are intended to meet the needs of both specialists in laser system design and those who use laser techniques in fundamental science and applied research

The book begins with the section devoted to new laser media and key components (ch

1 - ch 3), followed by theoretical and experimental studies the objective of which was to improve temporal and spatial performance of mid-infrared lasers (ch 4, ch 5) Novel schemes of side-pumped lasers are also considered in this part of the volume (ch 6, ch 7) Subsequent several chapters describe specific applications of solid-state lasers In particular, remote sensing, absolute distance measurement, and ignition of automobile engines are described in chapters 8 - 10

Nowadays, development of ultrafast laser systems, including amplification of ultrashort pulses to high energies, is based mainly on solid-state laser technology A substantial part of the volume is devoted to ultrafast phenomena Amplifying techniques, including regenerative amplification and optical parametric chirped-pulse amplification, are described in significant depth (ch 11 - ch 13) Modern methods of the femtosecond pulse characterization as well as the pulse shaping and spectrum control are also considered in detail (ch 14 - ch 18) Impressive achievements in femtosecond lasers intensify investigations in the scope of the high-field science In turn, advances in this area allow development of coherent radiation sources which simultaneously produce extremely short wavelength (reaching soft X-rays particularly by means of high-order harmonic generation) and feature the attosecond pulse duration Moreover, ultra-intense laser pulses provide new possibilities in the particle acceleration technique Chapters 19 - 25 cover fundamentals and development of the laser-based high-field science

This book is the result of efforts of experts from different countries I would like to acknowledge the authors for their contribution to the book I also wish to acknowledge Vedran Kordic for indispensable technical assistance in the book preparation and publishing

Editor

Mikhail Grishin

Institute of Physics and EKSPLA uab

Vilnius, Lithuania

Contents

1 Concentration-Dependent Laser Performance of Yb:YAG Ceramics

Jun Dong, Ken-ichi Ueda, Hideki Yagi and Alexander A Kaminskii

Yasushi Fujimoto

Efim Khazanov

4 Numerical Simulation of High-Power Operation

O A Louchev, Y Urata, M Yumoto, N Saito and S Wada

Jan K Jabczynski, Lukasz Gorajek, Waldemar Zendzian,

6 Efficient Intracavity Beam Combining of Multiple Lasers

Ming Lei

7 Compact, High Brightness and High Repetition Rate

Mikhail A Yakshin, Viktor A Fromzel, and Coorg R Prasad

8 In-line Typed High-Precision Polarization Lidar for Disaster Prevention 143

Tatsuo Shiina

9 Precision Dimensional Metrology based on a Femtosecond Pulse Laser 169

10 Micro-Solid-State Laser for Ignition of Automobile Engines 195

Masaki Tsunekane, Takayuki Inohara, Kenji Kanehara and Takunori Taira

11 High Gain Solid-State Amplifiers for Picosecond Pulses 213

Antonio Agnesi and Federico Pirzio

12 Dynamics of Continuously Pumped Solid-State

Mikhail Grishin and Andrejus Michailovas

13 Toward TW-Peak-Power Single-Cycle IR Fields

O D Mücke, S Ališauskas, A J Verhoef, A Pugžlys, A Baltuška,

V Smilgevičius, J Pocius, L Giniūnas, R Danielius, and N Forget

14 Measurement and Control of Carrier-Envelope Phase

Zhiyi Wei, Hainian Han, Wei Zhang, Yanying Zhao,

Jiangfeng Zhu, Hao Teng and Qiang Du

15 Pulse Measurement Techniques Using an Acousto-Optic

Nicolas Forget and Thomas Oksenhendler

16 Pulse-Shaping Techniques Theory and Experimental Implementations

T Oksenhendler and N Forget

17 Femtosecond Filamentation in Temperature Controlled Noble Gas 387

Zhenming Song, Yun Wei, Shiying Cao, Weipeng Kong,

Dongqing Pang, Ruxin Li, Qingyue Wang and Zhigang Zhang

18 Diffraction Gratings for the Selection of Ultrashort Pulses

Luca Poletto, Paolo Villoresi and Fabio Frassetto

Kenichi L Ishikawa

20 High-Order Harmonic Generation from Low-Density Plasma 465

Tsuneyuki Ozaki, Rashid Ganeev, Masayuki Suzuki and Hiroto Kuroda

21 An Attosecond Soft x-ray Nanoprobe:

Sarah L Stebbings, Jeremy G Frey and William S Brocklesby

22 Relativistic Nonlinear Thomson Scattering:

Kitae Lee, Sang-Young Chung, and Dong-Eon Kim

23 Radiation Dynamics from the Ultra-Intense Field Ionization of Atoms 539

Isaac Ghebregziabher and Barry Walker

Hans-Peter Schlenvoigt, Oliver Jäckel,

Sebastian M Pfotenhauer, and Malte C Kaluza

25 Laser-Driven Proton Acceleration Research and Development 609

Alexander S Pirozhkov, Hiroyuki Daido, Mamiko Nishiuchi and Koichi Ogura

Concentration-Dependent Laser Performance of Yb:YAG Ceramics and Passively Q-switched

Yb:YAG/Cr,Ca:YAG Lasers

Jun Dong1, Ken-ichi Ueda2, Hideki Yagi3 and Alexander A Kaminskii4

1Department of Electronic Engineering, Xiamen University

2Institute for Laser Science, University of Electro-Communications

3Konoshima Chemical Co Ltd

4Institute of Crystallography, Russian Academy of Science

1P R China 2,3Japan

4Russia

1 Introduction

Ytterbium doped laser materials have been intensely investigated for developing high power laser-diode pumped solid-state lasers around 1 μm (Krupke 2000) Yb:YAG as crystals and polycrystalline ceramics are one of the dominant laser gain media used for solid-state lasers (Lacovara et al., 1991; Brauch et al., 1995; Bruesselbach et al., 1997; Taira et al., 1997; Dong et al., 2006) owing to the excellent optical, thermal, chemical and mechanical properties (Bogomolova et al., 1976) Owing to the small radius difference between yttrium ions and ytterbium ions (Dobrzycki et al., 2004), Yb:YAG single-crystal doped with different

Yb concentrations can be grown by different crystal growth methods and efficient laser performance has been achieved (Brauch et al., 1995; Patel et al., 2001; Dong et al., 2006) Transparent laser ceramics (Lu et al., 2000; Lu et al., 2001; Lu et al., 2002; Takaichi et al., 2003; Dong et al., 2006) fabricated by the vacuum sintering technique and nanocrystalline technology (Yanagitani et al., 1998) have been proven to be potential replacements for counterpart single crystals because they have several remarkable advantages compared with single-crystal laser materials, such as high concentration and easy fabrication of large-size ceramics samples, multilayer and multifunctional ceramics laser materials (Yagi et al., 2006; Dong et al., 2007) Efficient and high power laser operation in Nd3+- and Yb3+-ions doped YAG ceramics has been demonstrated (Lu et al., 2002; Dong et al., 2006) Yb:YAG has been a promising candidate for high-power laser-diode pumped solid-state lasers with rod (Honea

et al., 2000), slab (Rutherford et al., 2000), and thin disk (Giesen et al., 1994; Stewen et al., 2000) configurations The quasi-three-level laser system of Yb:YAG requires high pumping intensity to overcome transparency threshold and achieve efficient laser operation at room temperature (Dong & Ueda 2005) The thin disk laser has been demonstrated to be a good way to generate high power with good beam quality owing to the efficiently cooling of gain medium and good overlap of the pump beam and laser beam (Giesen et al., 1994) However,

in the thin disk case, the pump beam must be folded many times into thin laser gain

medium disk with mirrors in order to absorb sufficient pump power, which makes the laser system extremely complicated Some applications require that the lasers should be compact and economic; therefore, the cooling system is eliminated in compact and easily maintainable laser system Therefore, laser-diode end-pumped microchip lasers are a better choice to achieve highly efficient laser operation under high pump power intensity The thinner the gain medium, the better the cooling effect, therefore, heavy doped Yb:YAG gain media are the better choice for such lasers The development of Yb:YAG ceramics doped with 1 at.% Yb3+ ions have been reported (Takaichi et al., 2003), but the efficiency of such Yb:YAG ceramic laser is low owing to the deficient activator concentration In principle, there is no concentration quenching effect in Yb:YAG, however, the unwanted impurities (such as Er3+, Tm3+, Ho3+, and so on) from raw materials will be deleterious to the laser performance owing to the high activator doping Concentration dependent optical properties and laser performance of Yb:YAG crystals have been reported(Yin et al., 1998; Qiu et al., 2002; Yang et al., 2002; Dong et al., 2007) The concentration quenching of Yb:YAG crystals has been investigated and it was found that fluorescence lifetime decreases when the Yb concentration is greater than 15 at.% and lifetime decreases up to 15% when the Yb concentration reaches to 25 at.% (Sumida & Fan 1994; Yang et al., 2002) The fluorescence lifetime of Yb3+ doped materials is usually affected by the radiative trapping and concentration quenching effects (M Ito et al., 2004) Radiative trapping and concentration quenching effects become stronger with Yb concentration and there is a concentration region (from 15 to 25 at.% for Yb:YAG crystal), two trends compete each other and consequently compensate each other, leading to a constant value of measured fluorescence lifetime Therefore special technologies have been taken to eliminate the radiative trapping effect when the fluorescence lifetime is measured for Yb doped materials Optical-thin samples or powder sandwiched between two undoped YAG crystals were used to measure the radiative lifetime of Yb:YAG crystals (Sumida & Fan 1994; Patel et al., 2001) The radiative lifetime of Yb:YAG crystal was found to decrease with Yb concentration Optical spectra of Yb:YAG ceramics doped with different Yb3+-lasant concentration (C Yb = 9.8, 12, and 20 at.%) and efficient 9.8 at.% Yb:YAG ceramic microchip lasers (Dong et al., 2006) have been reported recently The comparison of laser performance of Yb:YAG ceramic and single-crystal doped with 20 at.% Yb has been reported (Dong et al., 2007) However, there is no systematic comparison studies of microchip laser performance of Yb:YAG ceramics and single-crystal doped with different Yb concentrations

Compact, high beam quality laser-diode pumped passively Q-switched solid-state lasers with high peak power are potentially used in optical communications, pollution monitoring, nonlinear optics, material processing and medical surgery, and so on(Zayhowski 2000) Passively Q-switched solid-state lasers are usually achieved by using neodymium or ytterbium doped crystals as gain media and Cr,Ca:YAG as saturable absorber(Zayhowski & Dill III 1994; Lagatsky et al., 2000; Takaichi et al., 2002; Dong et al., 2006) or semiconductor saturable absorber mirror (SESAM)(Spuhler et al., 2001) as saturable absorber Compared with SESAM, Cr4+ doped bulk crystals as saturable absorber have several advantages, such

as high damage threshold, low cost, and simplicity The output pulse energy from passively Q-switched solid-state lasers is inversely proportional to the emission cross section of gain medium and reflectivity of the output coupler according to the passively Q-switched theory(Degnan 1995) Besides the broad absorption spectrum (Bruesselbach et al., 1997), longer fluorescence lifetime(Sumida & Fan 1994), high quantum efficiency (over 91% with

3 pump wavelength of 941 nm and laser wavelength of 1030 nm) (Fan 1993) of Yb:YAG gain medium and easy growth of high quality and moderate concentration crystal without concentration quenching (Patel et al., 2001), smaller emission cross section of Yb:YAG (about one tenth of that for Nd:YAG) (Dong et al., 2003) is more suitable to obtain high pulse energy output than Nd:YAG in passively Q-switched solid-state lasers Another interest in Yb:YAG lasers is that the frequency doubled wavelength of 515 nm matches the highest power line of Ar-ion lasers, thereby leading to the possibility of an all solid-state replacement (Fan & Ochoa 1995) Linearly polarized laser output was observed in these compact passively Q-switched lasers (Li et al., 1993; Yankov 1994; Kir'yanov et al., 1999; Yoshino & Kobyashi 1999; Dong et al., 2000; Bouwmans et al., 2001) The causes of the linearly polarized output in these passively Q-switched lasers were attributed to the influence of the pump polarization(Bouwmans et al., 2001), relative orientations of the switch and an intracavity polarizer(Kir'yanov et al., 1999), temperature change induced weak phase anisotropy(Yoshino & Kobyashi 1999), and the anisotropic nonlinear saturation absorption of Cr,Ca:YAG crystal under high laser intensity(Eilers et al., 1992) The anisotropic nonlinear absorption of Cr,Ca:YAG crystal induced linearly polarization in passively Q-switched lasers with Cr,Ca:YAG as saturable absorber held until appearing of transparent rare-earths doped YAG laser ceramics(Lu et al., 2002; Dong et al., 2006) Efficient laser operation in Nd3+:YAG and Yb3+:YAG ceramic lasers has been demonstrated(Lu et al., 2002; Dong et al., 2006; Nakamura et al., 2008) Chromium doped YAG ceramic has also been demonstrated to be a saturable absorber for passively Q-switched Nd:YAG and Yb:YAG ceramic lasers(Takaichi et al., 2002; Dong et al., 2006) Recently, laser-diode pumped passively Q-switched Yb:YAG/Cr:YAG all-ceramic microchip laser has been demonstrated(Dong et al., 2006), and pulse energy of 31 μJ and pulse width of 380 ps have been achieved with 89% initial transmission of the Cr,Ca:YAG ceramic as saturable absorber and 20% transmission of the output coupler However, there is coating damage occurrence because of the high energy fluence with low transmission of the output coupler There are two ways to solve the coating damage problem: one is to improve the coating quality on the gain medium which is costly; the other is to increase the transmission of the output coupler

to decrease the intracavity pulse energy fluence Therefore, 50% transmission of the output coupler was used to balance the output pulse energy and intracavity pulse energy, for this case, the initial transmission of Cr,Ca:YAG can be further decreased to obtain high energy output according to the passively Q-switched solid-state laser theory(Degnan 1995) The laser performance of passively Q-switched Yb:YAG/Cr,Ca:YAG all-ceramic microchip laser was further improved by using 20% initial transmission of the Cr,Ca:YAG ceramic as saturable absorber and 50% transmission of the output coupler, and no coating damage were observed with high pump power(Dong et al., 2007) Highly efficient, sub-nanosecond pulse width and high peak power laser operation has been observed in Yb:YAG/Cr4+:YAG composite ceramics(Dong et al., 2007; Dong et al., 2007) Although linearly polarized states was reported in passively Q-switched Nd:YAG/Cr,Ca:YAG ceramic lasers(Feng et al., 2004), the extinction ratio was very small The crystalline-orientation self-selected linearly polarized, continuous-wave operated microchip lasers were demonstrated by adopting [111]-cut Yb:YAG crystal(Dong et al., 2008) and [100]-cut Nd:YAG crystal(McKay et al., 2007)

as gain medium

Here, we report on the systematical comparison of the performance of miniature Yb:YAG

(C Yb = 9.8, 12, and 20 at.%) ceramic and Yb:YAG single-crystals (C Yb = 10, 15, and 20 at.%)

lasers at 1030 nm with two-pass pumping scheme The laser performance of Yb:YAG ceramics is nearly comparable to or better than their counterpart single crystals depending

on the Yb doping concentration The effect of Yb concentration on the optical-to-optical efficiency and laser emitting spectra was also addressed The polarization states of passively Q-switched Yb:YAG/Cr,Ca:YAG microchip lasers with Yb:YAG crystal or ceramic as gain medium and Cr,Ca:YAG crystal or ceramic as saturable absorber were also presented Based

on our previous experiments and results of passively Q-switched Yb:YAG/Cr,Ca:YAG microchip lasers, 20% initial transmission of the saturable absorber and 50% transmission of the output coupler were used in the experiments to compare the polarization states and the effect of the polarization states on the laser performance of these passively Q-switched microchip laser Linearly polarized states were observed in Yb:YAG/Cr,Ca:YAG combinations with at least one crystal For Yb:YAG/Cr,Ca:YAG all-ceramics combination, the laser oscillates at random polarization state The effect of polarized states of passively Q-switched Yb:YAG/Cr,Ca:YAG lasers on the laser performance was also investigated

2 Experiments

To compare the laser performance of Yb:YAG ceramics and single-crystals, double-pass pumped miniature lasers were used in the experiments To absorb sufficient pump power, high doping concentration was needed for thin gain medium Therefore, high doping concentration Yb:YAG single-crystals and ceramics were used in the laser experiments

Three Yb:YAG ceramics samples (CYb = 9.8, 12, and 20 at.%) were used in the laser

experiments Comparable Yb:YAG single-crystals (CYb = 10, 15, and 20 at.%) were used to compare the laser characteristics with those of Yb:YAG ceramics The size of the samples is

10 mm in diameter and 1 mm in thickness The absorption spectra of Yb:YAG crystals and ceramics were measured by using a ANDO white light source and an optical spectral analyzer (ANDO AQ6137) Emission spectra were measured at 900 – 1150 nm with a fiber-coupled diode laser operating at 940 nm as the pump source The pump light was focused into one of the ground surfaces of the sample close to the polished surface through which the emitted fluorescence was to be observed As a result the fluorescent light detected was generated close to the surface from which it exited the sample, such that it experienced minimal radiation trapping The fluorescence emission spectral signal was collected by using a focus lens and coupled into a multi-mode fiber which was connected to an optical spectral analyzer The resolution of the optical spectral analyzer is 0.01 nm The effective emission cross section of Yb:YAG crystals and ceramics was calculated by applying Fuechtbauer-Ladenburg formula The absorption and emission spectra of Yb:YAG ceramics and single-crystals doped with different ytterbium concentrations were measured at room temperature Fig 1 shows the room temperature absorption and emission spectra of Yb:YAG ceramic and single-crystal containing 20 at.% of ytterbium activators The absorption and emission spectra of Yb:YAG ceramics are nearly identical to those of Yb:YAG single crystals However there were some differences between Yb:YAG crystals and ceramics which may have potential effects on the laser performance Firstly, the absorption coefficient of Yb:YAG ceramics is higher than that of Yb:YAG single crystal for the same Yb doping concentration The peak absorption coefficient at 940 nm increases linearly with Yb activator concentration for both Yb:YAG ceramics and single-crystals, as shown in the inset

of Fig 1(a), the peak absorption coefficients at 940 nm of low doping concentraiton Yb:YAG samples were taken from Ref (Dong et al., 2003; Takaichi et al., 2003) However, the

5 absorption coefficient of Yb:YAG single-crystals increases slowly with Yb concentration compared to Yb:YAG ceramics And the absorption coefficient of Yb:YAG ceramics is about 10% more than that for the counterpart single-crystal with same doping levels at high doping levels This was caused by the segregation in Yb:YAG single crystal during the crystal growth and the Yb3+ concentration is lower than that in melt This effect becomes more obvious at high doping levels However, Yb3+ ions are uniformly distributed in the mixed Yb:YAG nanocrystalline power Secondly, there were some differences between the emission cross section of Yb:YAG ceramics and crystals Fig 1(b) shows the emission spectra

of Yb:YAG ceramic and single-crystals doped with 20 at.% Yb3+-ions Two main emission peaks are centered at 1030 nm and 1049 nm The effective peak emission cross section of Yb:YAG ceramics was estimated to be 2.2×10-20 cm2 at 1030 nm, which was lower than that

of Yb:YAG single-crystal (2.3×10-20 cm2) The effective emission cross section at 1047.5 nm (0.37×10-20 cm2) was about one sixth of that at 1030 nm for Yb:YAG ceramics However, the effective emission cross section at 1046.9 nm (0.39×10-20 cm2) of Yb:YAG crystal is 5% higher than that of Yb:YAG ceramics The lower effective emission cross section of Yb:YAG ceramics limits the laser performance under the same laser conditions as that for Yb:YAG crystals The emission cross section of Yb:YAG ceramics does not change with Yb concentration, which is in good agreement with the measured emission cross section of Yb:YAG single-crystals (Dong et al., 2003) although the emission intensity increases with increase of the Yb concentrations

0 5 10 15 20 25

2.5

(b)

Yb:YAG ceramics Yb:YAG crystals

nm and 1.03 μm The other surface was coated for total reflection at both 940 nm and 1.03

μm, acting as one cavity mirror and reflecting the pump power for increasing the absorption

of the pump power Plane-parallel fused silica output couplers with transmission (T oc) of 5 and 10% were mechanically attached to the gain medium tightly A 35-W high-power fiber-coupled 940 nm laser diode (Apollo, F35-940-1) with a core diameter of 100 μm and numerical aperture of 0.22 was used as the pump source Optical coupling system with two lenses M1 (8-mm focal length) and M2 (15-mm focal length) was used to focus the pump beam on the ceramic rear surface and to produce a pump light footprint on the Yb:YAG of about 170 μm in diameter The laser spectrum was analyzed by using an optical spectrum analyzer (ANDO AQ6137) with resolution of 0.01 nm Output beam profile of these lasers

was monitored by using a CCD camera, and beam quality factor, M2, was determined by measuring the beam diameters at different positions along the laser propagation direction

Fig 2 Schematic diagram of laser-diode pumped Yb:YAG ceramics and single-crystals miniature lasers DBS, dichroic beam splitter; OC, output coupler; M1, focus lenses with focal length of 8 mm; M2, focus lenses with focal length of 15 mm

Fig 3 Schematic diagram for passively Q-switched Yb:YAG microchip lasers with

Cr,Ca:YAG as saturable absorber OC, output coupler; PM, power meter

Fig 3 shows a schematic diagram of experimental setup for passively Q-switched Yb:YAG microchip laser with Cr,Ca:YAG as saturable absorber Two Yb:YAG samples are used as gain media, one is Yb:YAG ceramic doped with 9.8 at.% Yb, the other is [111]-cut Yb:YAG crystal doped with 10 at.% Yb The thickness of Yb:YAG samples is 1 mm, and the Yb:YAG samples are polished to plane-parallel One surface of the gain medium was coated for anti-reflection at 940 nm and total reflection at 1.03 μm acting as one cavity mirror The other surface was coated for high transmission at 1.03 μm Two 1-mm-thick, uncoated Cr,Ca:YAG ceramic and [111]-cut Cr,Ca:YAG crystal with 80% initial transmission, acting as Q-switch, was sandwiched between Yb:YAG sample and a 1.5-mm-thick, plane-parallel fused silica output coupler with 50% transmission Total cavity length was 2 mm The initial charge concentration of CaCO3 and Cr2O3 in growth of Cr,Ca:YAG crystal and fabrication of Cr,Ca:YAG ceramic are 0.2 at.% and 0.1 at.%, respectively The absorption center of Cr,Ca:YAG sample centered at 1 μm is also strongly affected by the annealing process and the exact concentration of this absorption center is difficult to determine, the concentration center of this absorption is roughly about 4% of the initial Cr doping concentration

Copper holder

M2 M1

Output DBS

7 (Okhrimchuk & Shestakov 1994) Therefore, the initial transmission of the Cr,Ca:YAG saturable absorber is usually used in comparing the laser performance of passively Q-switched lasers The initial transmission of Cr,Ca:YAG is governed by the doping concentration and the thickness of the sample, to fully compare laser performance with our previously passively Q-switched Yb:YAG/Cr,Ca:YAG all-ceramic microchip laser and the effect of polarization states on the passively Q-switched Yb:YAG/Cr,Ca:YAG microchip lasers, 1-mm-thick Cr,Ca:YAG crystal with 80% initial transmission was used in the experiment It should be noted that the polarization behavior keeps the same if a different modulation depth of Cr,Ca:YAG saturable absorber is used A high-power fiber-coupled 940

nm laser diode with a core diameter of 100 μm and numerical aperture of 0.22 was used as the pump source Two lenses of 8-mm focal length were used to focus the pump beam on the Yb:YAG rear surface and to produce a pump light footprint on the Yb:YAG of about 100

μm in diameter The laser was operated at room temperature The Q-switched pulse profiles were recorded by using a fiber-coupled InGaAs photodiode with a bandwidth of 16 GHz, and a 7 GHz Tektronix TDS7704B digital phosphor oscilloscope The laser spectrum was analyzed by using an optical spectrum analyzer The laser output beam profile was monitored using a CCD camera both in the near-field and the far-field of the output coupler

3 Results and discussion

3.1 Continuous-wave Yb:YAG miniature lasers

Fig 4 shows the output power of miniature Yb:YAG ceramics and single-crystal lasers as a

function of the absorbed pump power for different Yb concentrations and T oc The absorbed

pump power for reaching laser thresholds of Yb:YAG ceramics (CYb = 9.8, 12, and 20 at.%)

were 0.3, 0.33, and 0.64 W for T oc = 5% and 0.33, 0.5, 0.68 W for T oc = 10% The pump power

threshold increases with T oc and Yb concentration for Yb:YAG ceramic lasers This was

caused by the increase of the losses introduced by the large T oc and the increasing reabsorption of Yb3+ at lasing wavelength with Yb concentrations For Yb:YAG ceramics doped with different Yb concentrations, the output power increases linearly with absorbed

pump power for T oc = 5 and 10% The slope efficiencies respected to the absorbed pump

power for Yb:YAG ceramics (CYb = 9.8, 12, and 20 at.%) were measured to be 50, 55, and 45%

for Toc = 5% and 52, 44, and 38% for Toc = 10% Slope efficiency increases with T oc for 9.8 at.%

Yb:YAG ceramic, however, the slope efficiencies decrease with T oc for Yb:YAG ceramics doped with 12 and 20 at.% Yb3+ ions Maximum output power of 2.54 W was measured for

T oc = 5% by using 12 at.% Yb:YAG ceramic as gain medium when the absorbed pump power was 5.3 W The corresponding optical-to-optical efficiency was about 48%

The absorbed pump power for reaching laser thresholds of Yb:YAG single-crystal (CYb = 10,

15, and 20 at.%) were 0.3, 0.51 and 0.76 W for Toc = 5% and 0.35, 0.55, and 0.84 W for Toc =

10% The absorbed pump power threshold increases with the T oc and Yb concentrations, the same tendency as that for Yb:YAG ceramics However, the absorbed pump power thresholds of Yb:YAG single crystals were higher than those of Yb:YAG ceramics This may

be caused by the pump configuration used in the laser experiments and low pump power intensity with pump beam diameter of 170 μm Because the incident pump beam from laser-diode is several degrees away from the normal direction of the laser beam, there is a mismatch between the pump beam and laser beam From Fig 4 (b), we can see at low pump power just above absorbed pump power threshold, the laser performance is lower than that

0 1 2 3 4 5 60.0

Fig 4 Output power of (a) Yb:YAG ceramic and (b) Yb:YAG single crystal miniature lasers

as a function of absorbed pump power for different Yb concentrations and transmissions of the output couplings

high pump power levels, this is normal for the quasi-three-level system; efficient laser performance can be achieved at high pump power density (Dong & Ueda 2005) However, for Yb:YAG ceramics, owing to the random distribution of Yb:YAG crystalline particles, the absorbed pump power threshold can be achieved more easily Output power increases linearly with absorbed pump power for Yb:YAG single-crystals doped with 10 and 15 at.%

Yb The slope efficiencies of miniature lasers based on Yb:YAG single-crystals doped with 10

and 15 at.% Yb were measured to be 69, 62% for Toc = 5% and 67, 55% for Toc = 10% The slope efficiencies of Yb:YAG crystals doped with 10 and 15 at.% Yb3+ were higher than those for Yb:YAG ceramics although the pump power thresholds were higher than those of Yb;YAG ceramics At higher pump power density, the inversion population excited by the pump beam is well-over the threshold, and the modes matched very well, therefore, the laser oscillates at high slope efficiency, especially for Yb:YAG crystal doped with 10 and 15 at.% Yb The better laser performance of these crystals compared to their counterpart ceramic suggests that the intacavity loss for Yb:YAG crystal lower than that of Yb:YAG ceramics

For Yb:YAG single-crystal doped with 20 at.% Yb, the output power increases with the absorbed pump power, and tends to increase slowly when the absorbed pump power is

higher than a certain value (e.g 3 W for Toc = 5% and 2.3 W for Toc = 10%), as shown in Fig 4(b) However, besides the higher absorbed pump power threshold compared to its

counterpart Yb:YAG ceramic, the slope efficiencies (45% for T oc = 5% and 32 at.% for T oc =

10%) of 20 at.% Yb:YAG single crystal were lower than those (47% for T oc = 5% and 38 at.%

for T oc = 10%) for its counterpart Yb:YAG ceramic The laser results show that heavy doped

9 Yb:YAG ceramic is better than its single crystal counterpart The strong segregation of the impurities in Yb:YAG crystal with increase of the Yb concentration during crystal growth is the main reason for the worse laser performance The other reasons for the less efficient laser operation may be the impurities increases with doping concentration (Yin et al., 1998), the impurities induced concentration quenching effect limit the laser performance of highly doped Yb:YAG crystals The green emission was observed in the Yb:YAG crystals and ceramics when they were pumped with laser-diodes, and visible intensity increases with Yb concentration up to 15 at.% and then decreases with Yb concentration (Xu et al., 2005) Energy transfer from Yb3+ ions to Er3+ and Tm3+ impurities and cooperative energy transfer between Yb3+ ions are the causes of these visible luminescence These are deleterious to the infrared laser operation However, the distance between Yb3+ ions and impurities or other quenching centers is decreased with Yb concentration, the cooperative luminescence intensity decreases because the excited ions are more easily quenched by reaching a neighboring defect site Therefore, the effect of cooperative energy transfer is not a main factor to limit the laser performance of highly doped Yb:YAG crystals

010

Fig 5 Optical efficiencies of (a) Yb:YAG ceramic and (b) Yb:YAG single crystal miniature laser as a function of absorbed pump power for different Yb concentrations and

transmissions of the output coupler

Fig 5 shows the optical-to-optical efficiencies of Yb:YAG lasers as a function of absorbed pump power Under present laser experimental conditions, there is no saturation effect of Yb:YAG lasers with different output couplings for Yb concentration equal to or less than 15

at.% although the optical efficiency increases slowly with the absorbed pump power However, for 20 at.% Yb:YAG, there is saturation effect for ceramic lasers with T oc = 5% and for single-crystal lasers with different output couplings Maximum optical efficiency of 48% was achieved for Yb:YAG ceramic doped with 12 at.% Yb at the absorbed pump power of

5.3 W For single crystal doped with 20 at.% Yb lasants, there is a maximum optical efficiency for all output couplings [as shown in Fig 5(b)] The optical-to-optical efficiency decreases with further increase of the pump power For Yb:YAG ceramics, except the

comparable laser performance of 9.8 at.% Yb:YAG with T oc = 5 and 10%, the

optical-to-optical efficiency decreases with T oc and Yb concentration However, for Yb:YAG

single-crystals, the optical-to-optical efficiency decreases with the T oc and Yb concentration under different pump power levels Optical-to-optical efficiency of Yb:YAG crystal doped with less than 15 at.% Yb is higher than that for Yb:YAG ceramics under certain pump power levels For 20 at.% Yb:YAG, Yb:YAG ceramic has higher optical-to-optical efficiency than that of crystal under different pump power levels The decrease of the optical-to-optical efficiency

of Yb:YAG lasers with Yb concentration was attributed to the thick samples used for highly doped Yb:YAG samples The better laser performance can be further improved through optimizing the thicknesses for Yb:YAG samples with different Yb concentrations The highly efficient microchip lasers has been demonstrated by using the same crystals (Dong et al., 2007) as those here used

Fig 6 shows the maximum optical-to-optical efficiency under available pump power of Yb:YAG ceramics and single-crystals lasers as a function of Yb concentrations for different output couplings For Yb:YAG single crystals, the maximum optical-to-optical efficiency

decreases with Yb concentrations, there are 45% and 56% dropping for T oc = 5 and 10% when Yb concentration increases from 10 at.% to 20 at.% However, for Yb:YAG ceramics, the maximum optical-to-optical efficiency decreases with Yb concentration, the decrease is smaller for Yb:YAG ceramics compared to that for Yb:YAG single crystal There are 15 and

32% dropping for T oc = 5 and 10% when Yb concentration increases from 9.8 to 20 at.% for Yb:YAG ceramics Because small different optical properties were observed in Yb:YAG ceramics and single-crystals doped with different Yb concentrations(Dong et al., 2003; Dong

et al., 2006), the different laser performance of Yb:YAG ceramics and single-crystals may be caused by the Yb3+-ions distribution in YAG host and optical quality of Yb:YAG samples Although the distribution coefficient of Yb in Yb:YAG is close to unit, there is still concentration gradient observed in Yb:YAG single crystals along the growth axis and radius

of the crystal boule (Xu et al., 2003) The Yb3+-ion distribution inhomogeneity in Yb:YAG single-crystal becomes server with Yb concentration The impurities such as Ho3+, Er3+

increase with Yb concentration in Yb:YAG crystals because the strong segregation of earth ions in YAG crystal was observed This was observed in the reduced radiative lifetime

rare-in highly doped Yb:YAG crystals (Sumida & Fan 1994; Yrare-in et al., 1998; Patel et al., 2001) This concentration quenching effect limits the efficient laser performance of highly doped Yb:YAG crystals For ceramics, the distribution of Yb ions in the grains and grain boundary

is a main factor to determine the optical properties The gain boundary of YAG ceramics was measured to be less than 0.5 nm (Barabanenkov et al., 2004), and sintering temperature

is about 200 oC lower than the melt point of Yb:YAG crystal, the segregation of Yb in grain boundary can only be achieved by diffusion or migration, therefore the distribution of Yb in gain and boundary should be close to homogeneous When Yb ions were doped in YAG ceramics, the segregation of ytterbium ions in the grain boundary, accompanied by a reduction of the acoustic mismatch, leads to increased phonon transmission (Bisson et al., 2007) This will be further enhanced by introducing more ytterbium ions This may be one

of the main reasons for the better laser performance of heavy doped Yb:YAG ceramics compared to that of single-crystal with same doping levels

11

020406080

T oc = 10%:

Yb:YAG ceramic Yb:YAG crystal

T oc = 5%:

Yb:YAG Ceramic Yb:YAG Crystal

Fig 6 Comparison of the maximum optical-to-optical efficiency of Yb:YAG miniature lasers

as a function of Yb concentration The solid lines were used for illustration

Fig 7 shows the comparison of the laser emitting spectra of 9.8 at.% Yb:YAG ceramic and 10

at.% Yb:YAG single-crystal miniature lasers under different absorbed pump power for T oc =

5, and 10% Lasers operated at multi-longitudinal modes under different pump levels The number of longitudinal modes increases with the absorbed pump power because the inversion population provided with pump power can overcome the threshold for low gain away from the highest emission peak of Yb:YAG gain medium The longitudinal mode oscillation for these miniature Yb:YAG lasers was mainly caused by the etalon effect of plane-parallel Yb:YAG thin plate The separation of longitudinal modes was measured to be 0.29 nm, which is in good agreement with the free spectral range (0.292 nm) of 1-mm-long cavity filled with gain medium predicted by (Koechner 1999) Δλc= λ2 /2L c , where L c is the optical length of the resonator and λ is the laser wavelength And the center wavelength of the lasers shifts to longer wavelength with the pump power which is caused by the

temperature dependent emission spectra of Yb:YAG crystal (Dong et al., 2003) For T oc = 5%, both Yb:YAG ceramic and crystal lasers are oscillating at longer wavelength comparing to

those for T oc = 10% The cause of the wavelength shift to longer wavelength for T oc = 5% is relating to the change of the intracavity laser intensity (Kong et al., 2004) because only the

intracavity laser intensity is different for both cases Intracavity laser intensity for T oc = 5% is

about two times higher than that for T oc = 10%, therefore, more longitudinal modes will also

be excited for T oc = 5% Because the better laser performance for 10 at.% Yb:YAG lasers compared to 9.8 at.% Yb:YAG ceramics lasers, the intracavity intensity is higher for crystal laser, therefore Yb:YAG crystal lasers oscillate at longer wavelength than those for Yb:YAG

ceramics lasers, especially for T oc = 5% Strong mode competition and mode hopping in these Yb:YAG ceramic lasers were also observed When the laser oscillates, the excited Yb3+

ions jump back to the lower laser level, they always relax to other even-lower energy levels

or ground level, this process is rapid compare to the lifetime of Yb3+ ion in YAG crystal or ceramics The relaxation of Yb3+ ions to the lower energy or ground levels causes the lower-level population to increase with the lasing intensity, this increases the reabsorption This enhanced reabsorption provides a negative feedback process for the lasing modes and effective gain profile of Yb:YAG medium This negative feedback process accompanied with the effects of strong mode competition makes some stronger laser modes eventually faded

or quenched When the intracavity light intensity is high enough, the population distribution at lower energy levels is changed dramatically At the same time, the effective gain curve of Yb:YAG under lasing condition was altered by the strong reabsorption and temperature rise induced by the absorption pump power Some initially suppressed modes

at longer wavelength governed by the emission spectra can oscillate under changed gain curve, therefore the laser wavelength shifts to longer wavelength and mode hopping was observed Fig 8 shows the laser emitting spectra of 20 at% Yb:YAG ceramic and single-crystal miniature lasers under different pump power levels and output couplings The lasers oscillate at multi-longitudinal modes The number of the longitudinal modes increases with the pump power The laser oscillates at longer wavelength for 20 at.% Yb:YAG lasers compared to that for 10 at.% Yb:YAG lasers for both transmissions of the output couplers (as

shown in Fig 7 and Fig 8) The red-shift of laser wavelength for Toc = 10% with Yb

concentration is smaller than that for Toc = 5% because of the lower intracavity laser

intensity Yb:YAG lasers with T oc = 10% The number of longitudinal modes is larger for Toc =

5% than that for Toc = 10% This may be related to the gain curve change due to the strong reabsorption under strong intracavity intensity

The output beam transverse intensity profiles were also monitored in all the pump power range One example of the beam intensity profile at output power of 2.5 W for 12 at.%

Fig 7 Laser emitting spectra of 9.8 at.% Yb:YAG ceramic and 10 at.% Yb:YAG crystal

miniature lasers under different pump power levels, (a) T oc = 5%, (b) T oc = 10% The

resolution of the optical spectral analyzer is 0.01 nm

13

1028 1030 1032 1034 10361028 1030 1032 1034 1036

(b) (a)

ceramic crystal

Wavelength (nm)

Wavelength (nm)

Fig 8 Laser emitting spectra of 20 at.% Yb:YAG ceramic and crystal miniature lasers under

different pump power levels, (a) T oc = 5%, (b) T oc = 10% The resolution of the optical spectral analyzer is 0.01 nm

Yb:YAG ceramics with T oc = 5% was shown in Fig 9, as well as a horizontal slice through the center The output beam profile is close to TEM00 mode The measured spatial profile can be fitted with Gaussian function very well, as shown in Fig 9(b) Near-diffraction-limited beam

quality with M2 of less than 1.1 was achieved in these miniature lasers with Yb:YAG ceramics and single-crystals as gain media in the available pump power range

-1.5 -1.0 -0.5 0.0 0.5 1.0 1.50.0

0.20.40.60.8

1.0

Gaussian fit

Position (mm)

Fig 9 (a) Output laser beam profile of Yb:YAG ceramic miniature lasers when output power

is 2.5 W for 12 at.% Yb:YAG ceramics with T oc = 5% (b) Horizontal slice through center of beam profile with Gaussian fit

3.2 Passively Q-switched Yb:YAG/Cr,Ca:YAG microchip lasers

Four combinations of Yb:YAG and Cr,Ca:YAG were used in the laser experiments to investigate the polarization states of passively Q-switched Yb:YAG/Cr,Ca:YAG microchip

lasers: C1, Yb:YAG crystal + Cr,Ca:YAG crystal; C2, Yb:YAG ceramic + Cr,Ca:YAG ceramic; C3, Yb:YAG crystal + Cr,Ca:YAG ceramic; C4, Yb:YAG ceramic + Cr,Ca:YAG crystal The polarization states of passively Q-switched Yb:YAG/Cr,Ca:YAG microchip lasers with different combinations were investigated by measuring the output power after polarizer Table 1 summaries the polarization states observed in passively Q-switched Yb:YAG/Cr,Ca:YAG microchip lasers with different combinations of Yb:YAG, Cr,Ca:YAG crystals and ceramics By rotating the combination of Yb:YAG/Cr,Ca:YAG, the polarization states of these lasers do not change, only the polarization directions are changed by arranging Yb:YAG or Cr,Ca:YAG Rotating any one of sample does not affect the polarization states and no stronger influence on the polarization was observed

C1 Yb:YAG crystal + Cr,Ca:YAG crtstal Linear

C2 Yb:YAG ceramic + Cr,Ca:YAG ceramic Random

C3 Yb:YAG crystal + Cr,Ca:YAG ceramic Linear

C4 Yb:YAG ceramic + Cr,Ca:YAG crystal Linear

Table 1 Polarizations states of passively Q-switched Yb:YAG/Cr,Ca:YAG microchip lasers

Polarizer angle (Deg)

Fig 10 Polarization states of passively Q-switched Yb:YAG/Cr,Ca:YAG microchip lasers The solid lines show the sine function fitting of the experimental data

Fig 10 shows the typical polarization states of four combinations Except for the random oscillation of Yb:YAG/Cr,Ca:YAG all-ceramics combination, other three combinations exhibit linearly polarization output The extinction ratio of the linearly polarization is greater than 300:1 Some differences between the extinction ratios for different linearly polarization were observed The extinction ratios of three different linearly polarized

15 combinations are in the order of C1 > C4 > C3 The extinction ratios of three different linearly polarized combinations decrease a little with increase of the pump power, we did not observe significant decrease of the extinction ratio at the maximum pump power used here, this shows that the thermal effect under current available pump power is not strong enough to induce sufficient birefringence and depolarization for Yb:YAG crystals and ceramics However, we did observe the thermal effect under high pump power level for cw Yb:YAG microchip lasers(Dong et al., 2008), therefore, the thermal effect induced birefringence and depolarization should be considered in high power pumped passively Q-switched Yb:YAG/Cr,Ca:YAG microchip lasers The different polarization states between all-ceramics combination and three others are due to the random distribution of nanocrystalline particles in ceramics To fully understand the nature of polarization states in passively Q-switched Yb:YAG/Cr,Ca:YAG microchip lasers, we measured the polarization states of Yb:YAG crystals and ceramics by removing Cr,Ca:YAG saturable absorber and found that Yb:YAG crystals oscillate at linearly polarization states selected by the crystalline-orientations in the (111) plane(Dong et al., 2008) and Yb:YAG ceramic oscillates at unpolarization states Although there is saturation absorption in Cr,Ca:YAG ceramic, the same as that for Cr,Ca:YAG crystal, owing to the random distribution of Cr,Ca:YAG particles in ceramic, the saturation absorption does not exhibit crystalline-orientation dependent anisotropic properties when the sample is rotated, which is different from the anisotropic saturation absorption of Cr,Ca:YAG crystal when the laser propagate along [111] direction(Eilers et al., 1992) Therefore, the polarization states in passively Q-switched microchip lasers with Cr,Ca:YAG as saturable absorber are not only determined by the anisotropic saturation absorption of Cr,Ca:YAG saturable absorber, but also determined by the linearly polarized states of Yb:YAG crystals

The continuous-wave operation of Yb:YAG crystal and ceramic has been investigated previously by using different transmissions of output coupler(Dong et al., 2006; Dong et al., 2007) and found that the laser performance 1-mm-thick Yb:YAG crystal doped with 10 at.%

Yb is better than that of 1-mm-thick Yb:YAG ceramic doped with 9.8 at.% Yb The absorbed pump power thresholds are 0.46 W and 0.54 W for 1-mm-thick Yb:YAG crystal and ceramic, respectively, the slope efficiencies were 49% and 44%, respectively by using 50% transmission of output coupler The differences of cw laser performance between Yb:YAG crystal and ceramic suggest that the optical quality of ceramic used in the experiments is not

as good as that of Yb:YAG crystal, and the slight different doping concentration may be another cause of the difference

Here we show the effect of different polarization states of passively Q-switched Yb:YAG/Cr,Ca:YAG microchip lasers on the laser performance Average output power as a function of absorbed pump power for these four combinations of Yb:YAG and Cr,Ca:YAG microchip lasers was shown in Fig 11 The absorbed pump power thresholds were about 0.53, 0.66, 0.75, and 0.6 W for combinations C1, C2, C3 and C4 The higher pump power threshold of these passively Q-switched lasers was due to the low initial transmission of Cr,Ca:YAG and high transmission of the output coupler used in the experiments Average output power increases linearly with absorbed pump power for the four combinations, the slope efficiencies with respect to the absorbed pump power were estimated to be about 39,

36, 36 and 29% for the four combinations of C1, C2, C3 and C4, respectively The best laser performance (low threshold and high slope efficiency) of passively Q-switched Yb:YAG/Cr,Ca:YAG microchip lasers was obtained with C1 combination because of the enhancement of linearly polarized laser operation due to the combination of linearly

oscillation of Cr:YAG crystal under high intracavity laser intensity(Eilers et al., 1992) and the crystalline-orientation selected linearly polarized states of Yb:YAG crystal(Dong et al., 2008) Maximum average output power of 310 mw was obtained with Yb:YAG/Cr,Ca:YAG all-crystal combination when the absorbed pump power was 1.34 W, corresponding to optical-to-optical efficiency of 23% The optical-to-optical efficiency is 15% with respect to the incident pump power for C1 The optical-to-optical efficiencies with respect to the incident pump power were measured to be 12, 11 and 11% for C2, C3 and C4 respectively There is

no coating damage occurrence with further increase of the pump power owing to decrease

of the intracavity energy fluence by using high transmission output coupler

050100

Absorbed pump power (W)

Fig 11 Average output power as a function of the absorbed pump power for passively switched Yb:YAG/Cr,Ca:YAG microchip lasers with different combinations of Yb:YAG and Cr,Ca:YAG The solid lines show the linear fit of the experimental data

Q-Although linearly polarized laser operation was observed in Yb:YAG/Cr,Ca:YAG combinations with at least one crystal, the effect of linearly polarized states on the laser performance was different The slope efficiency of C4 is lower than that of C3, however the laser threshold of C4 is lower than that of C3 and the average output power is higher than that of C3 for all the available pump power range, as shown in Fig 11 The contribution of polarization states from Cr,Ca:YAG crystal and Cr,Ca:YAG ceramic is different, when Cr,Ca:YAG crystal is used as saturable absorber, even with Yb:YAG ceramic as gain medium, the laser threshold is low For all-ceramics combination, C2, although the laser threshold is higher than those of C1 and C4, the slope efficiency is better those of C4 and C3 These results show that the polarized states have great effect on the laser performance Even with random polarized states of all-ceramics combination, passively Q-switched Yb:YAG/Cr,Ca:YAG laser has nearly the same laser performance as that of all-crystals combination The discrepancies between all-crystals (C1) and all-ceramics (C2) combinations were caused by the optical quality of Yb:YAG crystal and Yb:YAG ceramic, the laser performance of Yb:YAG crystal is better than its ceramic counterpart The discrepancies

17 between C3 and C4 were attributed to the linearly polarization, with Cr,Ca:YAG crystal as saturable absorber, the extinction ratio of the polarization is stronger than that of with Cr,Ca:YAG ceramic as saturable absorber, the laser prefers to oscillate more efficiently with orientation selected anisotropic saturbable absorption of Cr,Ca:YAG crystal along <111> direction under high intracavity intensity(Eilers et al., 1992)

The output beam profile is close to fundamental transverse electro-magnetic mode Near diffraction-limited output beam quality with Mx2 of 1.05 and M2y of 1.04, respectively, was achieved in such compact passively-Q-switched Yb:YAG/Cr,Ca:YAG microchip lasers The output beam diameter near the output mirror was measured to be 100 μm

0.00.20.40.60.8

(b)

Fig 12 (a) Laser emission spectra under different average output powers in passively switched Yb:YAG/Cr,Ca:YAG all-ceramic microchip laser; (b) transmittance curves of 1-mm-thick Cr,Ca:YAG, 1.5-mm-thick fused silica output coupler, and their transmittance product Resonant modes are also plotted for illustration

Q-Owing to the broad emission spectrum of the Yb:YAG materials around 1.03 μm (about 10

nm in FWHM), many longitudinal modes can be excited even for a 1-mm-thick Yb:YAG crystal Microchip cw Yb:YAG lasers operate in a multi-longitudinal-mode over the whole pump power region(Dong et al., 2006) However, single-longitudinal-mode oscillation around 1029.7 nm was observed in passively Q-switched Yb:YAG/Cr,Ca:YAG microchip lasers when the average output power was kept below 50 mW for different Yb:YAG/Cr,Ca:YAG combinations, the same as that for all-ceramics combinations(Dong et al., 2007) Above this value, the laser exhibited two-mode oscillation and three-mode oscillation A typical example of single-longitudinal-mode and multi-longitudinal-mode oscillations of passively Q-switched Yb:YAG/Cr,Ca:YAG all-ceramic microchip laser under different average output power levels is shown in Fig 12(a) The separation between first and second modes was measured to be 1.16 nm, which is eight times wider than the free spectral range between the longitudinal modes (0.146 nm) in the laser cavity filled with gain medium predicted by(Koechner 1999) Δλc= λ2 /2L c , where L c is the optical length of the resonator and λ is the laser wavelength The separation between second and third modes was measured to be 0.3 nm, which is twice of that determined by the laser cavity The potential output longitudinal modes were selected by the combined etalon effect of the 1-mm-thick Cr,Ca:YAG as an intracavity etalon and 1.5-mm-thick fused silica output coupler

as a resonant reflector(Koechner 1999) Fig 12(b) shows the possible selected modes by the combining effect of 1-mm-thick Cr4+:YAG and 1.5-mm-thick fused silica The resonant modes, eight times of free spectral range (0.146 nm) away from the main mode centered at 1029.7 nm, will oscillate preferably because the wavelengths of these modes are very close to the high transmittance of the combined transmittance product The resonant mode will oscillate at 1030.87 nm due to the asymmetric gain profile centered at 1029.7 nm of Yb:YAG

At high pump power levels, besides the oscillation of the main mode depleting the inversion population and suppressing the oscillation of the resonant modes close to it, the local temperature rise induced by the pump power will change the transmittance of the etalons The relative gain and loss for different resonant modes will vary and determine the appearance of the third mode and elimination of the second mode The linewidth of each mode was less than 0.02 nm, limited by the resolution of optical spectra analyzer The central wavelength of 1029.7 nm shifts to longer wavelength with pump power, which is caused by the temperature dependent emission spectrum of Yb:YAG crystal(Dong et al., 2003) Therefore, stable single-longitudinal-mode oscillation can be maintained by increasing pump beam diameter incident on the laser medium at higher pump power The polarization states of passively Q-switched Yb:YAG/Cr,Ca:YAG microchip lasers have great effect on the characteristics of the output pulses Fig 13 shows the pulse characteristics (pulse repetition rate, pulse width, pulse energy and pulse peak power) of passively Q-switched Yb:YAG/Cr,Ca:YAG microchip lasers as a function of absorbed pump power For all four combinations of Yb:YAG and Cr,Ca:YAG, the repetition rate of passively Q-switched laser increases linearly with the absorbed pump power Pulse width (FWHM) of passively Q-switched Yb:YAG/Cr,Ca:YAG microchip lasers decreases with absorbed pump power at low pump power levels and tends to keep constant at high pump power levels The shortest pulse width of 277 ps was achieved with C4 combination Pulse widths for the four combinations are in the order of C4 < C1 < C2 < C3 Pulse energy increases with absorbed pump power and tends to keep constant at high pump power levels The highest pulse energy was achieved with C1 combination The pulse energy for the four

19 combinations are in the order of C1 > C4 > C2 > C3 Peak power of passively Q-switched Yb:YAG/Cr,Ca:YAG microchip lasers exhibits the same tendency as those of pulse energy: C1 > C4 > C2 > C3 for the four combinations Therefore, the overall best laser performance (highest peak power) in passively Q-switched Yb:YAG/Cr,Ca:YAG microchip lasers achieved by using C1 combination Linearly polarization operation of passively Q-switched all-crystals lasers is more favorable for laser performance The combination of Yb:YAG/Cr,Ca:YAG microchip lasers with Cr,Ca:YAG crystal as saturable absorber, C4, has better laser pulse characteristics than those of all-ceramics combination, C2 and combination C3 Although linearly polarized state was achieved in combination C3 with Yb:YAG crystal, the linearly polarized states was attributed to the linearly polarization of Yb:YAG crystal, not from the Cr,Ca:YAG ceramic The contribution of the linearly polarized state from Yb:YAG crystal in C3 combination is less than that from the nonlinear anisotropic absorption of Cr,Ca:YAG crystal, therefore, therefore, the laser performance of combination C3 is less than those of combination C1 and C4 The effect of depolarization effect on the polarization states observed in Yb:YAG crystal (Dong et al., 2008) may be another cause to less efficient laser operation in C3 combination at high pump power levels

0.6 0.8 1.0 1.2 1.4 30

C1 C2 C3 C4

Absorbed pump power (W)

Fig 13 Pulse characteristics (repetition rate, pulse width, pulse energy and peak power) of passively Q-switched Yb:YAG/Cr,Ca:YAG microchip lasers as a function of absorbed pump power for different combinations of Yb:YAG and Cr,Ca:YAG

4 Conclusions

In conclusion, systematic comparison of laser performance was done for Yb:YAG ceramics and single-crystals doped with different concentrations Although the pump power

thresholds of Yb:YAG crystals were higher than their ceramics counterparts due to the pump configuration, the efficient laser operation was obtained by using both Yb;YAG ceramics and single-crystals The laser performance of 1-mm-thick Yb:YAG ceramics and crystals becomes worse with Yb concentration under present miniature laser configuration However, the laser performance of Yb:YAG crystals is more sensitive to the Yb concentrations, while the laser performance of Yb:YAG ceramics is less sensitive to the Yb concentrations The laser performance of low doping Yb:YAG ceramics is worse than those obtaining from Yb:YAG singly crystals The laser performance of 20 at.% Yb:YAG ceramics

is better than its counterpart single crystal Both Yb:YAG ceramics and crystals miniature lasers oscillate at multi-longitudinal modes, the number of longitudinal-mode increases with absorbed pump power Strong mode competition and mode hopping were observed in these Yb:YAG lasers The strong reabsorption and gain curve change under high intracavity laser intensity play important roles on the red-shift of the output laser wavelength High

beam quality lasers with M2 less than 1.1 were achieved by adopting Yb:YAG ceramics and crystals as gain media Heavy-doped Yb:YAG ceramic will be a potential candidate for microchip lasers by optimizing the thickness and Yb3+ concentration

Random polarized oscillation was observed in passively Q-switched Yb:YAG/Cr,Ca:YAG all-ceramic microchip laser while linearly polarized oscillations were observed with at lease one crystal in the Yb:YAG/Cr,Ca:YAG combinations The polarization states in passively Q-switched Yb:YAG/Cr,Ca:YAG microchip lasers show that the linearly polarization states in passively Q-switched laser are not only resulted from the anisotropic saturation absorption

of Cr,Ca:YAG crystal, but also from linearly polarization states of Yb:YAG crystal High peak power pulses with sub-nanosecond pulse-width and nearly diffraction-limited beam quality were obtained in these lasers The best laser performance was achieved by using Yb:YAG crystal as gain medium and Cr,Ca:YAG crystal as saturable absorber because of the enhancement of linearly polarized state due to the crystalline-orientation selected polarized states of Yb:YAG crystal and linearly polarized oscillation of Cr,Ca:YAG crystal under high intracavity laser intensity Other combinations of Yb:YAG and Cr,Ca:YAG have less efficient linearly polarized laser oscillation and also affect the laser performance of passively Q-switched Yb:YAG/Cr,Ca:YAG microchip lasers

5 References

Barabanenkov, Y N., Ivanov, S N., Taranov, A V., Khazanov, E N., Yagi, H., Yanagitani,

T., Takaichi, K., Lu, J., Bisson, J F., Shirakawa, A., Ueda, K & Kaminskii, A A (2004) Nonequilibrium acoustic phonons in Y3Al5O12-based nanocrystalline

ceramics JETP Lett Vol 79, No 7, (342 - 345)

Bisson, J., Yagi, H., Yanagitani, T., Kaminskii, A., Barabanenkov, Y N & Ueda, K (2007)

Influence of the grain boundaries on the heat transfer in laser ceramics Opt Rev

Vol 14, No 1, (1 - 13)

Bogomolova, G A., Vylegzhanin, D N & Kaminskii, A A (1976) Spectral and lasing

investigations of garnets with Yb3+ ions Sov Phys JETP Vol 42, No 3, (440 - 446)

Bouwmans, G., Segard, B & Glorieux, P (2001) Polarisation dynamics of monomode

Nd3+:YAG lasers with Cr4+ saturable absorber: influence of the pump polarisation

Opt Commun Vol 196, No 1-6, (257 - 268)

21 Brauch, U., Giesen, A., Karszewski, M., Stewen, C & Voss, A (1995) Multiwatt diode-

pumped Yb:YAG thin disk laser continuously tunable between 1018 and 1053 nm

Opt Lett Vol 20, No 7, (713 - 715)

Bruesselbach, H W., Sumida, D S., Reeder, R A & Byren, R W (1997) Low-heat

high-power scaling using InGaAs-diode-pumped Yb:YAG lasers IEEE J Sel Top

Quantum Electron Vol 3, No 1, (105 - 116)

Degnan, J J (1995) Optimization of passively Q-switched lasers IEEE J Quantum Electron

Vol 31, No 11, (1890 - 1901)

Dobrzycki, L., Bulska, E., Pawlak, D A., Frukacz, Z & Wozniak, K (2004) Structure of YAG

crystals doped/substituted with erbium and ytterbium Inorg Chem Vol 43, No

24, (7656 - 7664)

Dong, J., Bass, M., Mao, Y., Deng, P & Gan, F (2003) Dependence of the Yb3+ emission cross

section and lifetime on the temperature and concentration in ytterbium aluminum

garnet J Opt Soc Am B Vol 20, No 9, (1975 - 1979)

Dong, J., Deng, P., Lu, Y., Zhang, Y., Liu, Y., Xu, J & Chen, W (2000) LD pumped

Cr4+,Nd3+:YAG with self-Q-switched laser output of 1.4 W Opt Lett Vol 25, No

15, (1101 - 1103)

Dong, J., Shirakawa, A., Takaichi, K., Ueda, K., Yagi, H., Yanagitani, T & Kaminskii, A A

(2006) All ceramic passively Q-switched Yb:YAG/Cr4+:YAG microchip laser

Electron Lett Vol 42, No 20, (1154 - 1156)

Dong, J., Shirakawa, A & Ueda, K (2008) A crystalline-orientation self-selected linearly

polarized Yb:Y3Al5O12 microchip laser Appl Phys Lett Vol 93, No 10, (101105)

Dong, J., Shirakawa, A., Ueda, K & Kaminskii, A A (2007) Effect of ytterbium

concentration on CW Yb:YAG microchip laser performance at ambient temperature

Part I: Experiments Appl Phys B Vol 89, No 2-3, (359 - 365)

Dong, J., Shirakawa, A., Ueda, K., Xu, J & Deng, P (2006) Efficient laser oscillation of

Yb:Y3Al5O12 single crystal grown by temperature gradient technique Appl Phys

Lett Vol 88, No 16, (161115)

Dong, J., Shirakawa, A., Ueda, K., Yagi, H., Yanagitani, T & Kaminskii, A A (2006)

Efficient Yb3+:Y3Al5O12 ceramic microchip lasers Appl Phys Lett Vol 89, No 9,

(091114)

Dong, J., Shirakawa, A., Ueda, K., Yagi, H., Yanagitani, T & Kaminskii, A A (2007)

Laser-diode pumped heavy doped Yb:YAG ceramic lasers Opt Lett Vol 32, No 13, (1890

-1892)

Dong, J., Shirakawa, A., Ueda, K., Yagi, H., Yanagitani, T & Kaminskii, A A (2007)

Near-diffraction-limited passively Q-switched Yb:Y3Al5O12 ceramic lasers with peak

power > 150 kW Appl Phys Lett Vol 90, No 13, (131105)

Dong, J., Shirakawa, A., Ueda, K., Yagi, H., Yanagitani, T & Kaminskii, A A (2007)

Ytterbium and chromium doped composite Y3Al5O12 ceramics self-Q-switched

laser Appl Phys Lett Vol 90, No 19, (191106)

Dong, J & Ueda, K (2005) Temperature-tuning Yb:YAG microchip lasers Laser Phys Lett

Vol 2, No 9, (429 - 436)

Dong, J., Ueda, K., Shirakawa, A., Yagi, H., Yanagitani, T & Kaminskii, A A (2007)

Composite Yb:YAG/Cr4+:YAG ceramics picosecond microchip lasers Opt Express

Vol 15, No 22, (14516 - 14523)

Eilers, H., Hoffman, K R., Dennis, W M., Jacobsen, S M & Yen, W M (1992) Saturation of

1.064 μm absorption in Cr,Ca:Y3Al5O12 crystals Appl Phys Lett Vol 61, No 25,

(2958 -2960)

Fan, T Y (1993) Heat generation in Nd:YAG and Yb:YAG IEEE J Quantum Electron Vol

29, No 6, (1457 -1459)

Fan, T Y & Ochoa, J (1995) Tunable single-frequency Yb:YAG laser with 1-W output

power using twisted-mode technique IEEE Photon Technol Lett Vol 7, No 10,

(1137 -1138)

Feng, Y., Lu, J., Takaichi, K., Ueda, K., Yagi, H., Yanagitani, T & Kaminskii, A A (2004)

Passively Q-switched ceramic Nd3+:YAG/Cr4+:YAG lasers Appl Opt Vol 43, No

14, (2944 - 2947)

Giesen, A., Hugel, H., Voss, A., Wittig, K., Brauch, U & Opower, H (1994) Scalable concept

for diode-pumped high-power solid-state lasers Appl Phys B Vol 58, No 5, (365 -

372)

Honea, E C., Beach, R J., S C Mitchell, Sidmore, J A., M A Emanuel, Sutton, S B., Payne,

S A., Avizonis, P V., Monroe, R S & Harris, D (2000) High-power dual-rod

Yb:YAG laser Opt Lett Vol 25, No 11, (805 - 807)

Kir'yanov, A V., Aboites, V & Ii'ichev, N N (1999) A polarisation-bistable noedymium

laser with a Cr4+:YAG passive switch under the weak resonant signal control Opt

Commun Vol 169, No 1-6, (309 - 316)

Koechner, W (1999) Solid State Laser Engineering Berlin, Springer-Verlag

Kong, J., Tang, D Y., Lu, J & Ueda, K (2004) Random-wavelength solid-state laser Opt

Lett Vol 29, No 1, (65 - 67)

Krupke, W F (2000) Ytterbium solid-state lasers - The first decade IEEE J Sel Top

Quantum Electron Vol 6, No 6, (1287 - 1296)

Lacovara, P., Choi, H K., Wang, C A., Aggarwal, R L & Fan, T Y (1991)

Room-temperature diode-pumped Yb:YAG laser Opt Lett Vol 16, No 14, (1089 - 1091)

Lagatsky, A A., Abdolvand, A & Kuleshov, N V (2000) Passive Q-switching and

self-frequency Raman conversion in a diode-pumped Yb:KGd(WO4)2 laser Opt Lett

Vol 25, No 9, (616 - 618)

Li, S., Zhou, S., Wang, P., Chen, Y C & Lee, K K (1993) Sefl-Q-switched

diode-end-pumped Cr,Nd:YAG laser with polarized output Opt Lett Vol 18, No 3, (203 -

204)

Lu, J., Prabhu, M., Song, J., Li, C., Xu, J., Ueda, K., Kaminskii, A A., Yagi, H & Yanagitani,

T (2000) Optical properties and highly efficient laser oscillation of Nd:YAG

ceramics Appl Phys B Vol 71, No 4, (469 - 473)

Lu, J., Prabhu, M., Song, J., Li, C., Xu, J., Ueda, K., Yagi, H., Yanagitani, T & Kaminskii, A

A (2001) Highly efficient Nd:Y3Al5O12 ceramic laser Jpn J Appl Phys Vol 40, No

6A, (L552 - L554)

Lu, J., Ueda, K., Yagi, H., Yanagitani, T., Akiyama, Y & Kaminskii, A A (2002)

Neodymium-doped yttrium aluminum garnet (Y3Al5O12) nanocrystalline ceramics -

a new generation of solid-state laser and optical materials J Alloys Compd Vol 341,

No 1-2, (220 - 225)

M Ito, C Goutaudier, Y Guyot, K Lebbou, T Fukuda & Boulon, G (2004) Crystal growth,

Yb3+ spectroscopy, concentration quenching analysis and potentiality of laser emission in Ca1-xYbxF2+x J Phys.: Condens Matter Vol 16, No 8, (1501 - 1521)

23

McKay, A., Dawes, J M & Park, J (2007) Polarisation-mode coupling in (100)-cut Nd:YAG

Opt Express Vol 15, No 25, (16342 - 16347)

Nakamura, S., Yoshioka, H., Matsubara, Y., Ogawa, T & Wada, S (2008) Efficient tunable

Yb:YAG ceramic laser Opt Commun Vol 281, No 17, (4411 - 4414)

Okhrimchuk, A G & Shestakov, A V (1994) Performance of YAG: Cr4+ laser crystal Opt

Mater Vol 3, No 1, (1 - 13)

Patel, F D., Honea, E C., Speth, J., Payne, S A., Hutcheson, R & Equall, R (2001) Laser

demonstration of Yb3Al5O12 (YAG) and materials properties of highly doped

Yb:YAG IEEE J Quantum Electron Vol 37, No 1, (135 - 144)

Qiu, H., Yang, P., Dong, J., Deng, P., Xu, J & Chen, W (2002) The influence of Yb

concentration on laser crystal Yb:YAG Mater Lett Vol 55, No 1-2, (1 - 7)

Rutherford, T S., Tulloch, W M., Gustafson, E K & Byer, R L (2000) Edge-pumped

quasi-three-level slab lasers: design and power scaling IEEE J Quantum Electron Vol 36,

No 2, (205 - 219)

Spuhler, G J., Paschotta, R., Kullberg, M P., Graf, M., Moser, M., Mix, E., Huber, G., Harder,

C & Keller, U (2001) A passively Q-switched Yb:YAG microchip laser Appl Phys

B: Lasers Opt Vol 72, No 3, (285 - 287)

Stewen, C., Contag, K., Larionov, M., Giessen, A & Hugel, H (2000) A 1-kW CW Thin Disc

laser IEEE J Sel Top Quantum Electron Vol 6, No 4, (650 -657)

Sumida, D S & Fan, T Y (1994) Effect of radiation trapping on fluorescence lifetime and

emission cross section measurements in solid-state laser media Opt Lett Vol 19,

No 17, (1343 - 1345)

Taira, T., Saikawa, J., Kobayashi, T & Byer, R L (1997) Diode-pumped tunable Yb:YAG

miniature lasers at room temperature: modeling and experiment IEEE J Sel Top

Quantum Electron Vol 3, No 1, (100 - 104)

Takaichi, K., Lu, J., Murai, T., Uematsu, T., Shirakawa, A., Ueda, K., Yagi, H., Yanagitani, T

& Kaminskii, A A (2002) Chromium-doped Y3Al5O12 ceramics - a novel saturable

absorber for passively self-Q-switched 1-μm solid-state lasers Jpn J Appl Phys

Vol 41, No 2A, (L96 - L98)

Takaichi, T., Yagi, H., Lu, J., Shirakawa, A., Ueda, K., Yanagitani, T & Kaminskii, A A

(2003) Yb3+-doped Y3Al5O12 ceramics - A new solid-state laser material Phys Status

Solidi (a) Vol 200, No 1, (R5 - R7)

Xu, X., Zhao, Z., Song, P., Jiang, B., Zhou, G., Xu, J., Deng, P., Bourdet, G., Chanteloup, J C.,

Zou, J & Fulop, A (2005) Upconversion luminescence in Yb3+ - doped yttrium

aluminum garnets Physica B Vol 357, No 3 -4, (365 - 369)

Xu, X., Zhao, Z., Zhao, G., Song, P., Xu, J & Deng, P (2003) Comparison of Yb:YAG crystals

grown by CZ and TGT method J Crystal Growth Vol 257, No 3-4, (297 - 300)

Yagi, H., Yanagitani, T., Yoshida, K., Nakatsuka, M & Ueda, K (2006) Highly efficient

flashlamp-pumped Cr3+ and Nd3+ codoped Y3Al5O12 ceramic laser Jpn J Appl

Phys Vol 45, No 1A, (133 - 135)

Yanagitani, T., Yagi, H & Hiro, Y (1998) Production of yttrium aluminium garnet fine

powders for transparent YAG ceramic Japan Patent 10-101411

Yang, P., Deng, P & Yin, Z (2002) Concentration quenching in Yb:YAG J Lumin Vol 97,

No 1, (51 - 54)

Yankov, P (1994) Cr4+:YAG Q-switching of Nd:host laser oscillators J Phys D Vol 27, No

6, (1118 - 1120)

Yin, H., Deng, P & Gan, F (1998) Defects in YAG:Yb crystal J Appl Phys Vol 83, No 7,

(3825 - 3828)

Yoshino, T & Kobyashi, Y (1999) Temperature characteristics and stabilization of

orthogonal polarization two-frequency Nd3+:YAG microchip lasers Appl Opt Vol

38, No 15, (3266 - 3270)

Zayhowski, J J (2000) Passively Q-switched Nd:YAG microchip lasers and applications J

Alloys Comp Vol 303-304, No (393 - 400)

Zayhowski, J J & Dill III, C (1994) Diode-pumped passively Q-switched picosecond

microchip lasers Opt Lett Vol 19, No 18, (1427 -1429)

New Infrared Luminescence

from Bi-doped Glasses

Fujimoto et al discovered a new infrared luminescent from bismuth-doped silica glass (BiSG)(Fujimoto & Nakatsuka 2001) Wide luminescent exists between 1000 and 1600 nm, and absorption is in the visible region The lifetime is 630 µs at room temperature Since this silica glass-based material has luminescence around 1.3 µm of zero-dispersion wavelength,

it can be used as a core material of an optical fiber amplifier for telecommunication in the 1.3-µm range Fujimoto et al also demonstrated an optical amplification at 1.3 µm with 0.8-

µm excitation(Fujimoto & Nakatsuka 2003) Therefore, BiSG is expected to be a promising substitution for Pr3+:ZBLAN fiber or Raman amplifiers in the 1.3-µm region

The spectroscopic properties of BiSG are different from previously reported Bi luminescent material(Fujimoto & Nakatsuka 2001), because the previous Bi-doped glasses or crystals with low Bi2O3 concentration showed that luminescences exist in the visible region (400 ~

600 nm) and that absorptions are in the ultraviolet region The lifetimes (~4 µs) are much shorter than those of BiSG at room temperature Such luminescences have been reported to originate from the Bi3+ ion in the media(M J Weber & Monchamp 1973; Parke & Webb 1973; van der Steen, van Hesteren et al 1981) BiSG is also different from the Bi2O3-rich glass whose Bi2O3 concentration ranges from 18.7 to 42.5 mol%(Sugimoto, Kanbara et al 1996) because the glass has no absorption in the visible region Then the investigation of new glass compositions with Bi luminescence is also progressing vigorously in a past decade Although the first discovered glass was a silica-based material with a SiO2 of 97.5 mol%(Fujimoto & Nakatsuka 2001), many glass compositions were tested and shown to effectively generate Bi luminescence, such as silicate(Peng, Qiu et al 2005; Ren, Yang et al 2006; Suzuki & Ohishi 2006; Arai, Suzuki et al 2007; Murata & Mouri 2007; Peng, Chen et al 2007; Ren, Qiu et al 2007; Zhou, Feng et al 2007; Peng, Wu et al 2008), germanate(Peng, Qiu

et al 2004; Meng, Qiu et al 2005; Peng, Meng et al 2005; Peng, Qiu et al 2005; Peng, Wang

et al 2005; Wang & Xia 2006; Xia & Wang 2006; Murata & Mouri 2007; Ren, Wu et al 2007;

Ren, Dong et al 2007; Ren, Qiao et al 2007; Ren, Qiu et al 2007; Ren, Qiu et al 2007; Peng,

Wu et al 2008; Qiu, Peng et al 2008), borate(Meng, Qiu et al 2005; Murata & Mouri 2007; Qiu, Peng et al 2008), germanosilicate(Ren, Dong et al 2007; Ren, Dong et al 2008), and phosphate(Meng, Qiu et al 2005; Qiu, Peng et al 2008) glasses

In this chapter, the author will introduce the basic properties of Bi doped silica glass (BiSG), such as a phase diagram and spectroscopic properties, and then mainly talk about the origine of luminescent center

2 Basic properties of BiSG

2.1 Phase diagram

A phase diagram of BiSG was obtained for the Bi2O3-Al2O3-SiO2 glass system Silica powder (Aerosil 50; SiO2, 99.8%), bismuth-oxide (Kojundo Chemical Lab Co., Ltd.; α-Bi2O3, 99.99%), and aluminum oxide (Kojundo Chemical Lab Co., Ltd.; α-Al2O3, 99.99%) were used as reagents A properly mixed powder was inserted into a silica tube with an inner/outer diameter of 1/3 mmφ, and then the tube was heated by a mixed gas burner of natural gas and oxygen After heating, the powder was checked for a distinctive glassy wetting If it had such wetting, the composition was determined to be the glassy phase in the Bi2O3-Al2O3-SiO2 glass system

The measured phase diagram of the Bi2O3-Al2O3-SiO2 glass system is shown in Fig 1 The circle, triangle, and cross points show the glassy wetting states (pink to reddish-brown), unclear glassy states (pink to reddish-brown), and no glassy state (reddish-brown), respectively This phase diagram shows a tendency where the glass whose Al2O3 content is larger than Bi2O3 is well glassified above a 90% SiO2 concentration On the other hand, all the samples are glassified at a 80% SiO2 concentration without dependence on the Bi2O3 or

Al2O3 content The infrared luminescent spectrum is observed until 10 mol% of Bi2O3

15 20

2.2 Influence of additives on luminescent intensitys

The Bi2O3-Al2O3-SiO2 glass system is affected by alkaline metal additive Figure 2 shows an effect of Li2O additive in BiSG The glass composition is Bi2O3(1.0 mol%)-Al2O3(7.0 mol%)-SiO2(92-x mol%)-Li2O(x mol%) glass system The luminescent intensity decreases with increasing Li2O additive drastically (Seo, Fujimoto et al 2006) Therefore, in order to get luminescent center, we should carefully choose the host composition

0 10 20 30 40 50 60 70

Fig 2 Luminescent intensity dependence on Li2O concentration for Bi2O3(1.0

mol%)-Al2O3(7.0 mol%)-SiO2(92-x mol%)-Li2O(x mol%) glass system

0 5 10 15 20 25

BiSG_0.1_xx BiSG_1.0_xx

GeO 2 concentration [mol%]

Fig 3 Dependence of lumienscent intensity on GeO2 additive The filled circle denotes BiSG with 0.1 mol% Bi2O3 concentration, while the filled square represents that of 1.0 mol% Bi2O3

concentration The nomenclature of the samples is as follows: for example, the sample name

“BiSG_1.0_5.0” means that the composition is Bi2O3 = 1.0 mol%, GeO2 = 5.0 mol%

On the other hand, GeO2 is the one of attractive additive to increase luminescent intensity of BiSG (Fujimoto, Hirata et al 2007) Figure 3 shows the dependence of luminescent intensity on GeO2 concentration All the samples contain 7.0 mol% of Al2O3 The nomenclature of the samples is as follows: for example, the sample name “BiSG_1.0_5.0” means that the composition is Bi2O3 = 1.0 mol%, GeO2 = 5.0 mol% The luminescent intensity of BiSG grows with increasing GeO2 concentration almost linearly for BiSG_0.1_xx samples, and the luminescent intensity of BiSG_0.1_5.0 is 26.3 times larger than that of BiSG_0.1_0.0 only because of the GeO2 additive The increment effect on BiSG with GeO2 additive is also observed for a Bi2O3 concentration of 1.0 mol% (BiSG_1.0_5.0), but it is less remarkable than for the lower Bi2O3 concentration of 0.1 mol% Furthermore, the increment is only about 1.5 times larger than for BiSG without GeO2 (BiSG_1.0_0.0) On the other hand, the luminescent intensity of BiSG_0.1_5.0 is almost same as that of BiSG_1.0_0.0 According to these data, the GeO2 additive effectively increases the luminescent intensity of BiSG, and this effect is especially remarkable at low Bi2O3 concentrations

2.3 Spectroscopic properties

The typical spectroscopic properties of BiSG are shown in Fig 4 Five main absorption bands exist between 250 and 2000 nm: 300 (A), 500 (B), 700 (C), 800 (D), and 1000 nm (E) (Fig 5(a)) It is considered that absorption band A is mainly derived from O2- in the base glass(Scholze 1991) The other four absorptions (B~E) are connected to the infrared emissions shown in Fig 5(b) Each luminescent peak wavelength and full width at half maximum (FWHM) were recognized as 1182 and 300 nm at 500-nm excitation, 1144 and 192

nm at 700 nm, 1265 and 336 nm at 800 nm, and 1130 and 188 nm at 1000 nm A similarity of the luminescent spectra can be seen between 700- and 1000-nm excitations These spectroscopic properties are different from the Bi3+ ones(M J Weber & Monchamp 1973; Parke & Webb 1973; van der Steen, van Hesteren et al 1981)(Table 1)

Bi3+:Glass*1 (Na2O•P2O5) Bi

3+:Crystal*2 (Bi3Ge4O12) BiSG *3

*1 (Parke & Webb 1973), *2 (M J Weber & Monchamp 1973), *3 (Fujimoto & Nakatsuka 2001) Table 1 Differences of spectroscopic properties between BiSG and previously reported Bi3+

luminescent material

3 The origin of luminescent center

After the discovery of a new infrared luminescent bismuth center, several research groups try to understand what is the origine of the luminescence Although there have been many previous discussions on this distinctive luminescent center, it has remained unclear Different authors tentatively assigned the different origins of this near infrared luminescence to the electronic transition derived from Bi5+(Fujimoto & Nakatsuka 2001; Dvoyrin, Mashinsky et al 2006; Fujimoto & Nakatsuka 2006; Wang & Xia 2006; Xia & Wang 2006; Ohkura, Fujimoto et al 2007), Bi2+(Ren, Qiu et al 2007; Ren, Qiu et al 2007; Ren, Qiu et

al 2007; Ren, Dong et al 2008), and Bi+(Meng, Qiu et al 2005; Meng, Qiu et al 2005;

0 20 40 60 80 100

(a)

0 20 40 60 80 100 120

500nm_ex 700nm_ex 800nm_ex 1000nm_ex

Dvoyrin, Mashinsky et al 2006; Arai, Suzuki et al 2007; Ren, Qiu et al 2007; Ren, Qiu et al 2007; Ren, Qiu et al 2007; Yang, Chen et al 2007; Zhou, Feng et al 2007; Qiu, Peng et al 2008; Ren, Dong et al 2008; Truong, Bigot et al 2008) or to that of BiO molecules(Ren, Yang

et al 2006; Murata & Mouri 2007; Peng, Chen et al 2007; Peng, Wu et al 2008) dispersed in the glass host Since most of these proposals were however analogized from only spectroscopic mesurement analysis, uncertainty remains in the present discussions In addition, even the same researchers offer several explanations, suggesting that spectroscpic analogy is insufficient to correctly understand the luminescent center or the luminescent mechanism

Based on this viewpoint, our group discarded the spectroscopic analogical approach to understand the structure of the luminescent center or its mechanism and instead chose such instrumental analytical approaches as nuclear magnetic resonance (NMR), x-ray diffraction (XRD), electron spin resonance (ESR), x-ray photoelectron spectroscopy (XPS), and extended x-ray absorption fine structure (EXAFS) NMR data revealed the coordination structure of the specific ions in a material, ESR and XPS data provided the valence state of ions, and EXAFS offered the bonding distance between the specific and neighboring ions Once these analytic instrumental data are integrated to build one possible figure of a luminescent center, then the luminescent mechanism will be discussed, because knowledge of the luminescent center is very useful for understanding the luminescent mechanism, which is obviously important for such optical applications as lasers or amplifiers

In the following paragraphs, let’s try to build up an image of the local structure of the Bi luminescent center based on the analytical data, such as, spectroscopic properties (SPCT), luminesent intensity (LMI), NMR, XRD, ESR, XPS, and the EXAFS data of BiSG in a simple

Bi2O3-Al2O3-SiO2 glass system without discrepancies From this approach, we will reach one strongly possible local structure of a distinctive Bi luminescent center that consists of Bi and

Al that exist closely to each other

3.1 Sample preparation

In these analyses, composition of BiSG is very important, because Bi infrared luminescent center, as shown in section 2.2, is disappeared with increasing some additives in the host This means that majority part of Bi ions in the host shifts to non-emissive site, thus even if

we choose the multi-component glass system and analyze the Bi centers, we could not judge the results form an inherent luminescent center or the other non-emissive site, then we would go into the complicated maze Therefore, the analyses should be carried out to concentrate on the simple three components system, Bi2O3-Al2O3-SiO2 glass system

The samples for the instrumental analyses were prepared as follows

1 A-series: The ratio of Bi2O3 to Al2O3 was kept at 3/7, and the Bi2O3 concentration varied from 0.1, 0.3, 0.5, 1.0, and 3.0 mol% These samples were called A1-A5, respectively Their compositions are inside the glassy phase area in Fig 1

2 B-series: B1 was composed of Bi2O3 (1.0 mol%), Al2O3 (7.0 mol%), and SiO2 (92.0 mol%) This was used for the measurement of the spectroscopic properties because Al2O3-rich BiSG includes few bubbles B2 was composed of Bi2O3 (0.3 mol%), Al2O3 (2.3 mol%), and SiO2 (97.4 mol%) and B3 of Bi2O3 (3.0 mol%), Al2O3 (7.0 mol%), and SiO2 (90.0 mol%) They were used for the ESR measurements

3 C-series: C1 was composed of Bi2O3 (1.0 mol%) and SiO2 (99.0 mol%) without Al2O3, and C2 was composed of Al2O3 (2.3 mol%) and SiO2 (97.7 mol%) without Bi2O3 C1 and C2 were dark brown and colorless, respectively C1 had no glassy wetting, but C2 did The chemical composition of the investigated BiSG samples and the several standards are listed in Table 2 Silica powder (Aerosil 50; SiO2, 99.8%), bismuth-oxide (Kojundo Chemical Lab Co., Ltd.; α-Bi2O3, 99.99%), and aluminum oxide (Kojundo Chemical Lab Co., Ltd.; α-

Al2O3, 99.99%) were used as reagents to make the glass samples of the Bi2O3-Al2O3-SiO2

glass system The mixtures of these powders were melted in an aluminum crucible in an electric furnace at 1750°C in air, and the melts were annealed by natural cooling All of these glasses were reddish-brown NaBiO3 (Kanto Chemical Co., Inc.; >80%), which was identified

as NaBiO3•2H2O by XRD(PDF#30-1161 2000), α-Bi2O3, and Bi-metal (Kojundo Chemical Lab Co., Ltd.; 99.9%) were used as standard materials for the analyses